Alkali metal intercalation

Many layered metal chalcogenides may be used as a cathodic (positive) insertion elecUode in rechargeable alkali metal batteries because of their ability to reversibly intercalate alkali metal cations [11,12,96], Any useful electrode material must fulfill most of the following requirements ... 

Graphite reacts with alkali metals, for example potassium, to form compounds which are non-stoichiometric but which all have limiting compositions (for example K C) in these, the alkaU metal atoms are intercalated between the layers of carbon atoms. In the preparation of fluorine by electrolysis of a molten fluoride with graphite electrodes the solid compound (CF) polycarbon fluoride is formed, with fluorine on each carbon atom, causing puckering of the rings. 

Among the alkali metals, Li, Na, K, Rb, and Cs and their alloys have been used as exohedral dopants for Cgo [25, 26], with one electron typically transferred per alkali metal dopant. Although the metal atom diffusion rates appear to be considerably lower, some success has also been achieved with the intercalation of alkaline earth dopants, such as Ca, Sr, and Ba [27, 28, 29], where two electrons per metal atom M are transferred to the Cgo molecules for low concentrations of metal atoms, and less than two electrons per alkaline earth ion for high metal atom concentrations. Since the alkaline earth ions are smaller than the corresponding alkali metals in the same row of the periodic table, the crystal structures formed with alkaline earth doping are often different from those for the alkali metal dopants. Except for the alkali metal and alkaline earth intercalation compounds, few intercalation compounds have been investigated for their physical properties. 

Raman spectra have also been reported on ropes of SWCNTs doped with the alkali metals K and Rb and with the halogen Br2 [30]. It is found that the doping of CNTs with alkali metals and halogens yield Raman spectra that show spectral shifts of the modes near 1580 cm" associated with charge transfer. Upshifts in the mode frequencies are observed and are associated with the donation of electrons from the CNTs to the halogens in the case of acceptors, and downshifts are observed for electron charge transfer to the CNT from the alkali metal donors. These frequency shifts of the CNT Raman-active modes can in principle be u.sed to characterise the CNT-based intercalation compound for the amount of intercalate uptake that has occurred on the CNT wall. 

Doping of alkali-metals into CNTs has been examined [11]. The X-ray powder diffraction (XRD) patterns of the K- or Rb-doped CNTs show that alkali-metals are intercalated between the CNT layers. The hexagonal unit cell is essentially the same as that of the stage-1 alkali-metal intercalated graphite ACg (A=K, Rb). For a sample doped with Rb, the observed lattice parameter of the perpendicular... 

As future outlook, it would be of great relevance to be able to eventually enhanee the intrinsic conductivity of CNTs. In this respect, the latest development in alkali metal intercalated CNTs looks rather promising. In faet, Chauvet et al. recently sueeeeded to dope aligned CNT by potassium and found that the Pauli susceptibility increases a factor of 3 upon doping, indicating that K-doped tubes are still good eonductors [23]. 

Tanuma, S., Synthesis and structure of quasi-one-dimensional carbon crystal carbolite and intercalation with alkali metals and halogens. In Supercarbon, Synthesis, Properties and Applications, ed. S. Yoshimura and R. P. H. Chang, Springer-Verlag, Heidelberg, 1998, pp. 120 127. 

Cj(K prepared — the first alkali metal-graphite intercalation compound. 

Figure 8.16 Layer-plane sequence along the c-axis for graphite in various stage I -5 of alkali-metal graphite intercalation compounds. Comparison with Fig. 8.15 shows that the horizontal planes are being viewed diagonally across the figure. /,. is the interlayer repeat distance along the c-axis.

Whereas the electrochemical decomposition of propylene carbonate (PC) on graphite electrodes at potentials between 1 and 0.8 V vs. Li/Li was already reported in 1970 [140], it took about four years to find out that this reaction is accompanied by a partially reversible electrochemical intercalation of solvated lithium ions, Li (solv)y, into the graphite host [64], In general, the intercalation of Li (and other alkali-metal) ions from electrolytes with organic donor solvents into fairly crystalline graphitic carbons quite often yields solvated (ternary) lithiated graphites, Li r(solv)yC 1 (Fig. 8) [7,24,26,65,66,141-146],... 

First reported by Fredenhagen in 1926 F3, F4), the graphite-alkali-metal compounds possess a relative simplicity with respect to other intercalation compounds. To the physicist, their uncomplicated structure and well defined stoichiometry permit reasonable band-structure calculations to be made S2,12) to the chemist, their identity as solid, "infinite radical-anions frequently allows their useful chemical substitution for such homogeneous, molecular-basis reductants as alkali metal-amines and aromatic radical anions N2, B5). 

Tributsch H (1982) Photoelectrochemical Energy Conversion Involving Transition Metal d-States and Intercalation of Layer Compounds. 49 127-175 Truter MR (1973) Structures of Organic Complexes with Alkali Metal Ions. 16 71-111 Tytko KH, Mehmke J, Kurad D (1999) Bond Length-Bond Valence Relationships, With Particular Reference to Polyoxometalate Chemistry. 93 1-64 Tytko KH (1999) A Bond Model for Polyoxometalate Ions Composed of M06 Octahedra (MOk Polyhedra with k > 4). 93 65-124... 

Metal chalcogenides, apart from their technological significance in industrial applications, have played an important role in the development of new synthetic concepts and methods in the area of solid-state chemistry. A great example is alkali metal intercalation into TiS2 (Chap. 6) first reported three decades ago, which highlighted the then-novel synthetic approach called soft chemistry chimie douce). This low-temperature process allows for new compounds to be obtained while retaining the structural framework of the precursor. Related to this concept is the... 

Layered dichalcogenides, such as sulfides or selenides of Ti, Mo, W, Zr, Ta, Nb, V, and Cr, are able to dissolve certain alkali metal ions and in some cases posttransition (pseudo-alkali) metal ions (Cu, Ag ), via a mechanism in which the guest is inserted between the dichalcogenide layers. Lithium ion intercalation into TiS2, which among layered dichalcogenides has been one of the most prominent cathode... 

Protons are not the sole species that can be incorporated into the lattices of different host materials. At the beginning of the 1960s, Boris N. Kabanov showed that during cathodic polarization of different metals in alkaline solutions, intercalation of atoms of the corresponding alkali metal is possible. As a result of such an electrochemical intercalation, either homogeneous alloys are formed (solid solutions) or heterogeneous polyphase systems, or even intermetallic compounds, are formed. 

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